CN102935367B - A kind of C 5hydrogenation of petroleum resin Catalysts and its preparation method - Google Patents
A kind of C 5hydrogenation of petroleum resin Catalysts and its preparation method Download PDFInfo
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Abstract
The invention provides a kind of C
5hydrogenation of petroleum resin catalyst, comprises Metal Palladium on described complex carrier of Alumina-titanium oxide composite carrier and load and metal molybdenum or tungsten; In described complex carrier, the weight ratio of aluminium oxide and titanium oxide is 3: 1-6: 1; The content of Metal Palladium is 0.2-0.4% based on the weight of described catalyst; And Metal Palladium and metal molybdenum or be 1: 0.8-2 with the weight ratio of tungsten.This catalyst is used for C
5petroleum Resin Hydrogenation Process not only has low temperature hydrogenation activity, also has good anti-impurity ability and good stability.The present invention is also corresponding provides a kind of C
5the preparation method of hydrogenation of petroleum resin catalyst.
Description
Technical field
The present invention relates to a kind of C
5hydrogenation of petroleum resin Catalysts and its preparation method, is specifically related to a kind of palladium series hydrocatalyst and preparation method thereof.
Background technology
Along with the development of China's oil chemical industry, the production capacity of ethene also increases year by year.C
5petropols are the accessory substance C with ethylene unit
5cut is primary raw material, the polymer that the solid-state or thick relative molecular mass be polymerized in the presence of a catalyst is lower, and its average molecular mass is generally between 1000-3000.This resin price is cheap, has the excellent performance such as acidproof, alkaline-resisting and anti-aging, is therefore widely used in the aspects such as adhesive tape, thermosol, road coating, ink and rubber.Existing C
5petropols are generally in rufous, and softening point is at about 120 DEG C; But along with the development in each field of industry, people are to the quality of Petropols, and especially its form and aspect and softening point require more and more higher; The such as field such as thermosol and paint of coating needs sharp increase to the low white high-quality Petropols of softening point; And rufous C
5petropols range of application is very limited.Therefore, external many companies take hydrogenation technique to make C
5petropols are converted into C
5hydrogenated petroleum resin.
C
5hydrogenated petroleum resin makes C by catalytic hydrogenation
5double bond in Petropols is saturated, and deviates from halogen element that resin remains in the course of the polymerization process and obtain.Catalytic hydrogenation improves colourity and the photo and thermal stability of resin, solves C
5the smell of Petropols and oxidation-stabilized sex chromosome mosaicism, widened C greatly
5the application of Petropols.C
5hydrogenated petroleum resin is widely used in adhesive, traffic paint, the every profession and trade such as ink and rubber.According to external experience, C
5hydrogenation of petroleum resin will be China C
5petropols realize seriation, commercial important channel, are also the important means of increasing economic efficiency; Therefore, C is accelerated
5the research and development of hydrogenated petroleum resin are very important.
Owing to producing C
5during Petropols, the reason of raw material and polymerization technique, there is double bond in it, and containing halide, hydrogen sulfide, part synthesis technique also has gel to generate, therefore, and C
5hydrogenation of petroleum resin difficulty is very large.The existing catalyst system used is mainly noble metal and the large class of base metal two.The C that prior art Literature is introduced
5hydrogenation of petroleum resin catalyst has Ni/Al
2o
3, Pd/Al
2o
3, Ni/Si etc.As patent CN100389874C discloses a kind of C
5hydrogenation of petroleum resin catalyst, be namely carrier with aluminium oxide, take palladium as active component, its weight percentage is 1-1.5%; Catalyst promoter X
1for one or more in lithium, sodium, potassium, its weight percentage is 0.5-5%; Auxiliary agent X
2for molybdenum and/or tungsten, its weight percentage is 1-5%.During described catalyst application, hydrogenation temperature is 150-300 DEG C, and pressure is 10-20Mpa, liquid hourly space velocity (LHSV) 0.5-1.5h
-1, hydrogen/oil mol ratio is 0.5-2.5.This invention solves domestic C 5 petroleum resin hydrogenation plant and all adopts import palladium series catalyst and derivative costly large with cost problem; But this catalyst is when applying, it is carry out hydrogenation reaction under higher temperature and pressure that process conditions require, such process conditions make hydrogenation plant energy and material consumption very high, and operating cost is very large.
There is provided a kind of preparation method of C 5 hydrogenated petroleum resin for another patent CN200510080028, the temperature of its hydrogenation reaction is 150-350 DEG C, and pressure is 6-20Mpa, and liquid air speed is 0.5-2h
-1; Preferable reaction temperature is 280-320 DEG C, and pressure is 10-17Mpa.The catalytic hydrogenation component weight ratio wherein adopted is: catalyst carrier alumina is 100 parts, and palladium content is 0.8 part, and transition metal copper content is 0.2 part, and rare earth metal cerium content is 0.5 part, and the 4th major element Theil indices is 1 part.This catalyst application, in C 5 petroleum resin hydrogenation, obtains that bromine valency is low, form and aspect are low, and outward appearance is colourless product.But hydrogenation reaction temperature and pressure is higher equally in that patent, and energy consumption is large.
China is to C
5the research of hydrogenation of petroleum resin catalyst is started late, current domestic C
5hydrogenation of petroleum resin all uses import palladium series catalyst; Therefore, be badly in need of C
5the innovation research of hydrogenation of petroleum resin catalyst.Because C 5 petroleum resin is a kind of heat-sensitive substance, the research and development of the catalyst with low temperature hydrogenation activity are seemed particularly important.
Summary of the invention
Inventor is to C
5hydrogenation of petroleum resin catalyst has carried out research extensively and profoundly, found that use complex carrier, and in active component, use bimetallic component can contribute to the distribution of Metal Palladium on carrier, increases concerted catalysis effect.Such catalyst is used for C
5petroleum Resin Hydrogenation Process not only has low temperature hydrogenation activity, also has good anti-impurity ability and heat endurance.
The invention provides a kind of C
5hydrogenation of petroleum resin catalyst, comprises Metal Palladium on described complex carrier of Alumina-titanium oxide composite carrier and load and metal molybdenum or tungsten; In described complex carrier, the weight ratio of aluminium oxide and titanium oxide is 3: 1-6: 1; The content of Metal Palladium is 0.2-0.4% based on the weight of described catalyst; And Metal Palladium and metal molybdenum or be 1: 0.8-1: 2 with the weight ratio of tungsten.Wherein, the content of preferable alloy palladium is 0.25-0.3% based on the weight of described catalyst, and Metal Palladium and metal molybdenum or be 1: 1-1: 1.5 with the weight ratio of tungsten.
Different from patent described in background technology, the present invention adopts bi-component complex carrier, supported bi-metallic catalysis, and the catalyst developed is for C
5hydrogenation of petroleum resin, applicable pressure is reduced to 3-8MPa, and operating temperature is 70-150 DEG C; Namely catalyst of the present invention has low-temperature catalytic activity, thus requires lower to hydrogenation plant; And it is extremely beneficial to the hydrogenation of this heat-sensitive substance of C 5 petroleum resin.In addition, in the present invention, the content (weight based on described catalyst is 0.2-0.4%) of precious metal palladium is lower, is conducive to the cost control of catalyst.
Preferred catalyst specific surface provided by the invention is 70-210m
2/ g, pore volume is 0.6-1.6ml/g.The specific surface of further preferred described catalyst is 120-200m
2/ g, pore volume is 0.65-0.9ml/g.Catalyst specific surface provided by the invention and pore volume depend primarily on specific area and the pore volume of selected alumina support, select the specific area of suitable size and the alumina support of pore volume and control in conjunction with the roasting degree of depth can make catalyst provided by the invention have better active and stability.
The present invention also provides a kind of C
5the preparation method of hydrogenation of petroleum resin catalyst, comprising: steps A, under pH value 4-5 by Alumina-titanium oxide composite carrier palladium salting liquid and tungstenic solution or containing the mixed solution of molybdenum solution in flood; With step B, the complex carrier that will be impregnated with active component is dry, and at the roasting temperature of 300-800 DEG C.
Preferably in preparation method of the present invention, the preparation method of described Alumina-titanium oxide composite carrier before steps A is: impregnated in titanium salt solution by alumina support at the temperature of 80 DEG C, impregnated aluminium oxide is dry at 100-120 DEG C, then obtain complex carrier at the roasting temperature of 300-700 DEG C.Wherein total pore volume volume of preferred described alumina support is less than or equal to described titanium salt solution volume, obtains comprehensive titanium dipping to make alumina support.Preferred described titanium salt solution is the acetate of titanium, sulfate or nitrate solution.
Preferably in preparation method of the present invention, total pore volume volume of described Alumina-titanium oxide composite carrier is less than or equal to the volume of mixed solution used in steps A, is fully immersed on complex carrier to make active component.Wherein, dipping method is divided into saturated infusion process and filters infusion process two kinds, and the former is after measuring the saturated water absorption of carrier, and required metal component is mixed with the amount of solution that energy loaded body just absorbs completely, after dipping, namely solid drying and roasting obtain catalyst; The latter is that preparation is greater than the maceration extract of carrier saturated extent of adsorption, and after dipping, solid after filtration, namely dry and roasting obtain catalyst.Because hydrogenation of petroleum resin belongs to the fast reaction process that diffusion controls, so the active component palladium of catalyst and molybdenum or tungsten are preferably distributed in the outer surface of carrier granular, and the distribution in shell, greatly can improve the utilization rate of catalytic activity and metal active constituent like this.Thus comparatively preferred infusion process is saturated infusion process.
In the preparation method of catalyst of the present invention, preferred palladium salting liquid used is palladium bichloride, palladium nitrate or palladium sulfate solution, wherein more preferably palladium chloride solution; Tungstenic solution used is tungstates or tungsten oxide solution, wherein more preferably ammonium metatungstate solution; Used is molybdate or molybdenum oxide solution containing molybdenum solution, wherein more preferably ammonium molybdate solution.
In preparation method of the present invention, described in preferred steps A, be the aqueous solution of mass concentration 0.5-0.7% containing molybdenum solution and described tungstenic solution.
Catalyst of the present invention is used for C
5hydrogenation of petroleum resin has following outstanding feature: the first, and the low temperature hydrogenation activity of catalyst of the present invention is high; The second, catalyst of the present invention has good anti-impurity ability, can use by long period.
Detailed description of the invention
Bromine valency: bromine valency is for weighing presence of unsaturates in oil samples, and the grams of the bromine consumed with 100 grams of oil samples represents; Bromine valency is higher, and contained by oil samples, unsaturated hydrocarbons is more.It detects and adopts quality of chemical products index, namely adopts small-hole drilling to analyze oil samples.
We use hydrogenation conversion to describe the hydrotreated lube base oil degree of product usually; Hydrogenation conversion=[(raw material bromine valency-product bromine valency)/raw material bromine valency] * 100%.
The detection of specific surface and pore volume: comprise the specific surface of aluminium oxide, complex carrier and catalyst and the detection of pore volume.Method for detecting specific area adopts multiple spot BET method, uses F-sorb2400 specific surface area analysis instrument to detect; The detection method of pore volume adopts static capacity method, uses V-sorb2800 pore volume detector to detect.
The detection of palladium, molybdenum, W content in product catalyst: use inductively coupled plasma atomic emission spectrum to detect.
The present invention describes the present invention in detail by following examples, can make the present invention of those skilled in the art comprehend, but these embodiments does not form any restriction to scope of the present invention.
In following examples, Alumina-titanium oxide composite carrier selects trifolium-shaped, but those skilled in the art are known, and this complex carrier can be granular, bar-shaped, cylindrical etc.The peripheral radius of trifolium-shaped carrier is about 3mm.In the preparation method of catalyst of the present invention, the manufacturer of aluminium oxide used is not particularly limited.
In following examples, method for preparing catalyst is: at the temperature of 80 DEG C, aluminium oxide is flooded 3-6 hour in titanium salt solution, filtration leaches, and at the temperature of 100-120 DEG C dry 8-10 hour, then the roasting temperature 3-6 hour acquisition Alumina-titanium oxide composite carrier of 300-700 DEG C, wherein the weight ratio of aluminium oxide and titanium oxide is 3: 1-6: 1.By gained Alumina-titanium oxide composite carrier under pH value 4-5 in palladium salting liquid and tungstenic solution or containing the mixed solution of molybdenum solution in flood 4-6 hour, filtration leaches, complex carrier dry 6-10 hour at the temperature of 100-120 DEG C of active component will be impregnated with, then at the roasting temperature 4-7 hour acquisition catalyst of the present invention of 300-800 DEG C.
Embodiment 1
The preparation of carrier: be 180m by 100g specific surface
2/ g and pore volume are that the 0.8g/ml dilution heat of sulfuric acid (wherein the weight concentration of dilute sulfuric acid aqueous solution is about 10%) of the trifolium-shaped aluminium oxide 100ml titanium sulfate of 0.74ml/g floods 4 hours, drying 10 hours at the temperature of 120 DEG C, at the roasting temperature 6 hours of 700 DEG C, obtain 126.7g Alumina-titanium oxide composite carrier 1, wherein the weight ratio of aluminium oxide and titanium oxide is 4: 1.
The preparation of catalyst: be that the complex carrier 1 of 0.72ml/g immerses 85ml chloride containing palladium 0.51g/ml and containing in the mixed aqueous solution of ammonium molybdate 0.006g/ml by 100g pore volume, flood after 4 hours, drain away the water, with the hydrazine hydrate reduction 2 hours that 120ml concentration is 40%, spend deionized water, until there is no chlorion, then at the temperature of 110 DEG C dry 5 hours, in the roasting temperature 6 hours of 700 DEG C, obtain catalyst.Wherein palladium content is 0.3% of total catalyst weight, and molybdenum content is 0.3% of total catalyst weight.Catalyst specific surface is 166m
2/ g, pore volume is 0.68ml/g.
The inspection of catalyst effect: catalyst of the present invention is used for C
5petroleum Resin Hydrogenation Process, hydroconversion condition and reaction result as follows:
Embodiment 2
The preparation of carrier: be 178m by 180g specific area
2/ g and pore volume are that the trifolium-shaped aluminium oxide 142ml of 0.76ml/g floods 4 hours containing the cyclohexane solution of tetraethyl titanate 1.25g/ml, at the temperature of 110 DEG C dry 6 hours, at the roasting temperature 5 hours of 700 DEG C; Obtain the Alumina-titanium oxide composite carrier of 240g, wherein the weight ratio of aluminium oxide and titanium oxide is 3: 1.
The preparation of catalyst: be that the complex carrier 2 of 0.72ml/g immerses 92ml chloride containing palladium 0.64g/ml and containing in the mixed aqueous solution of ammonium molybdate 0.007g/ml by 120g pore volume, flood after 5 hours, drain away the water, with the hydrazine hydrate reduction 2 hours that 120ml concentration is 40%, spend deionized water, until there is no chlorion, then at the temperature of 110 DEG C dry 4 hours, in the roasting temperature 6 hours of 700 DEG C, obtain catalyst.Wherein palladium content is 0.28% of total catalyst weight, and molybdenum content is 0.34% of total catalyst weight.Catalyst specific surface is 175m
2/ g, pore volume is 0.7ml/g.
Embodiment 3
The preparation of carrier: be 180m by 175g specific surface
2/ g and pore volume are that the 0.62g/ml cyclohexane solution of the trifolium-shaped aluminium oxide 135ml tetraethyl titanate of 0.74ml/g floods 4 hours, drying 9 hours at the temperature of 120 DEG C, at the roasting temperature 6 hours of 500 DEG C, obtain 205g Alumina-titanium oxide composite carrier, wherein the weight ratio of aluminium oxide and titanium oxide is 6: 1.
The preparation of catalyst: be that the complex carrier 1 of 0.72ml/g immerses 96ml chloride containing palladium 0.64g/ml and containing in the mixed aqueous solution of ammonium metatungstate 0.005g/ml by 120g pore volume, flood after 6 hours, drain away the water, with the hydrazine hydrate reduction 2 hours that 120ml concentration is 40%, spend deionized water, until there is no chlorion, then at the temperature of 120 DEG C dry 6 hours, in the roasting temperature 7 hours of 600 DEG C, obtain catalyst.Wherein palladium content is 0.3% of total catalyst weight, and W content is 0.45% of total catalyst weight.Catalyst specific surface is 172m
2/ g, pore volume is 0.71ml/g.
The inspection of catalyst effect: catalyst of the present invention is used for C
5petroleum Resin Hydrogenation Process, hydroconversion condition and reaction result as follows:
Catalyst life is evaluated: take C 5 petroleum resin as raw material, catalyst in the present embodiment is loaded in fixed bed reactors and carries out catalytic hydrogenation reaction, and with the hydrogenation conditions catalytic reaction identical with above table after 1000 hours, product bromine valency becomes 0.54gBr/100g oil from 0.42gBr/100g oil.
Embodiment 4
The preparation of carrier: be 180m by 95g specific surface
2/ g and pore volume are that the 0.69g/ml cyclohexane solution of the trifolium-shaped aluminium oxide 100ml tetraethyl titanate of 0.74ml/g floods 3 hours, drying 8 hours at the temperature of 120 DEG C, at the roasting temperature 5 hours of 600 DEG C, obtain 119.5g Alumina-titanium oxide composite carrier 4, wherein the weight ratio of aluminium oxide and titanium oxide is 4: 1.
The preparation of catalyst: be that the complex carrier 1 of 0.7ml/g immerses 85ml chloride containing palladium 0.51g/ml and containing in the mixed aqueous solution of ammonium metatungstate 0.006g/ml by 100g pore volume, flood after 6 hours, drain away the water, with the hydrazine hydrate reduction 2 hours that 120ml concentration is 40%, spend deionized water, until there is no chlorion, then at the temperature of 110 DEG C dry 5 hours, in the roasting temperature 4 hours of 800 DEG C, obtain catalyst.Wherein palladium content is 0.3% of total catalyst weight, and W content is 0.3% of total catalyst weight.Catalyst specific surface is 164m
2/ g, pore volume is 0.67ml/g.
Comparative example 1
The preparation of catalyst: adopt the trifolium-shaped alumina support identical with embodiment 4, but do not carry out the dipping of tetraethyl titanate and carrier is single aluminium oxide.Adopt the method identical with embodiment 4 to flood in palladium bichloride and ammonium metatungstate solution and wash dry and roasting, preparing the catalyst that load on alumina support has palladium and tungsten.Wherein palladium content is 0.3% of total catalyst weight, and W content is 0.3% of total catalyst weight.Catalyst specific surface is 164m
2/ g, pore volume is 0.51ml/g.
Catalyst life is evaluated: by the catalyst obtained in this comparative example, and with raw material in the same manner as in Example 3 and hydrogenation conditions reaction, catalytic reaction is after 1000 hours, and product bromine valency becomes 4.7gBr/100g oil from 2.1gBr/100g oil.
Known from the life assessment contrast embodiment 3 and comparative example 1, in the present invention, the life-span of catalyst is long, and catalyst anti-impurity ability is strong.Containing plurality of impurities in material carbon 5 petroleum resin, due to the bimetallic component energy imurity-removal of catalyst in the present invention, and comparatively large then its duct of catalyst pore volume is not easily blocked by impurity and affects catalyst activity, thus finally makes catalyst life long.
Claims (10)
1. a C
5hydrogenation of petroleum resin catalyst, is made up of Metal Palladium on described complex carrier of Alumina-titanium oxide composite carrier and load and metal molybdenum or tungsten; In described complex carrier, the weight ratio of aluminium oxide and titanium oxide is 3:1-6:1; The content of Metal Palladium is 0.2-0.4% based on the weight of described catalyst; And Metal Palladium and metal molybdenum or be 1:0.8-1:2 with the weight ratio of tungsten; Active component palladium and molybdenum or tungsten are distributed in the outer surface of carrier granular, and the distribution in shell.
2. catalyst according to claim 1, is characterized in that, the content of Metal Palladium is 0.25-0.3% based on the weight of described catalyst, and Metal Palladium and metal molybdenum or be 1:1-1:1.5 with the weight ratio of tungsten.
3. catalyst according to claim 1 and 2, is characterized in that, the specific surface of described catalyst is 70-210m
2/ g, pore volume is 0.6-1.6ml/g.
4. catalyst according to claim 3, is characterized in that, the specific surface of described catalyst is 120-200m
2/ g, pore volume is 0.65-0.9ml/g.
5., as a preparation method for catalyst as described in any one in claim 1-4, comprising:
Steps A: under pH value 4-5 by Alumina-titanium oxide composite carrier palladium salting liquid and tungstenic solution or containing the mixed solution of molybdenum solution in flood;
Step B: the complex carrier that will be impregnated with active component is dry, and at the roasting temperature of 300-800 DEG C.
6. preparation method according to claim 5, it is characterized in that, before steps A, the preparation method of Alumina-titanium oxide composite carrier is: impregnated in titanium salt solution by alumina support at the temperature of 80 DEG C, impregnated aluminium oxide is dry at 100-120 DEG C, then obtain complex carrier at the roasting temperature of 300-700 DEG C.
7. preparation method according to claim 6, is characterized in that, total pore volume volume of described alumina support is less than or equal to described titanium salt solution volume.
8. according to the preparation method in claim 5 to 7 described in any one, it is characterized in that, total pore volume volume of described Alumina-titanium oxide composite carrier is less than or equal to the volume of mixed solution used in steps A.
9. preparation method according to claim 5, is characterized in that, described palladium salting liquid is palladium chloride solution in step, and described tungstenic solution is ammonium metatungstate solution, and described is ammonium molybdate solution containing molybdenum solution.
10. preparation method according to claim 5, is characterized in that, in step the described aqueous solution being mass concentration 0.5-0.7% containing molybdenum solution and described tungstenic solution.
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| CN104174409A (en) * | 2013-05-23 | 2014-12-03 | 中国石油化工股份有限公司 | Petroleum resin hydrogenation catalyst and application thereof |
| CN107880159A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of two-part preparation method of hydrogenated petroleum resin |
| CN107876051A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation of petroleum resin palladium series catalyst, preparation method and applications |
| CN106914259A (en) * | 2017-03-17 | 2017-07-04 | 钦州学院 | A kind of method of hydrotreating of C 5 petroleum resin |
| CN110237843A (en) * | 2018-03-09 | 2019-09-17 | 中国石油化工股份有限公司 | A kind of nickel catalyst and its preparation method and application |
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